Vat dye of the anthraquinone series.



TATES ra'rnn anion.

WILHELM nnnznnne AND WALTER nation, or ser ousness, NEAR mnn fassrsnons 'To ACTIEN ensnnnsonnrr run ANILIN FABBIKATION; F

- BERLIN, GERMANY.

.VA'J. DYE OF THE ANTHRAQUINONF- fiERIES.

1i! 0 Drawing.-

Specification of Letters Eatent.

Patented May 30, 1911.

To all wiwm it may concern:

Be it'known that we, WILHELM HERZBERG and WALTER BRUCE, subjects of the Emperor of Germany, residing at Schoneberg, near Berlin, Germany, our post-office addresses bein'g Landshuterstrasse 24 and Neue Culmstrasse 5 respectively,

new and useful Improvements in New Vat Dyes of the Anthraquinone Series, of which the following is a specification.

According to our present invention new dyes 'ofnthe .anthraquinone series can' be manufactured which or on-benzylidene beta-aminoanthraquinone may probably possess the following constitution:

s--o o6n.

As to the 'tints'produced by the new dyes, very clear and intense shades of a very good fastness may products of shades vary fromyellow to orange to brown.

Application filed January 30, 1911. Serial No 605 10.

Scht'meberg, near Berlin, Germany, have invented certain I contain sulfur and dye cotton without a moidant in a suitable-vat; on the observation I A mixture of 50' partsarts of ben zaldehyde solution;

. beta-aminoanthraquinone. be obtained with thenew l our present invention which As to the production of the parent-mate'- rials for the new=manufacture-, these may be obtained by acting with benzaldehyde or with a benzyl halid or-a benzal halid or-a derivative of one of these :bodies on alpha- IBEBLIN, GER- aminoanthraquinone or a derivative thereof (except an amino derivative) or a beta-. aminoanthraquinone or a derivative thereof. It may also-be statedthat'it 'is not necessary to isolate the parent material thus obtained which is to be used in the new manufacture in any suitable case the formation" of the benzylidene or benzyl compound may be combined with the production of the new sulfur compound in one operation. a

In giving hereafter; an example for the manufacture of the parent material we wish to state that-we do-not claim anymanufacturerelating to this'parent material.

I of beta-aminoan thraquinone and '50 p is gradually heated until the aldehyde boils.

hen the evolution of water vapor ceased the mass isldistilled in avac'uum in order to eliminate 'the excess of hyde. quinone is thus obtainedina pure state as a yellow body melting at 189 C. It dissolves has benzalde- The benzylidene-beta-aminoanthrain concentrated sulfuric acid to a yellow.

it is difiicultly soluble in alcohol, more-soluble in benzene and easily soluble in glaciab acetic acid. Other --benzylidene derivatives ofbeta-aminoanthraquinone or of a derivative of a beta-aminoanthraquinone be correspondingly obtained. Thus may be produced, for instance, the monobenzylidene derivative of 2.6 diaminoanthraquinone, which melts at about 240250 C. and is an orange-yellow'powder.- Likewise the. m no-benzylidene-27-diaminoanff thra-quinone may be obtained by acting with Tbenzaldehyde corresponding proport on on-2.7 diamino-anthraquinone;- this new benzylidenedder-ivative melts at-"about 140 C.- and is a brownish-yellow powder soluble in concentrated-sulfuric acid to a yellow solution. Furthermore, the benzyl derivative of beta-aminoanthraquinone may be 0btained by acting with benzyl-chlorid upon This new product is a yellow powder melting at about 27 5 C: which dissolves in concentrated sulfuric acid to a'yellow solution. Other benzyl derivatives of beta-aminoanthraquinones or of alpha-aminoanthraquinone may be obtained in a like manner.

In order to illustrate our invention, we ing by weight:

(1.) 104 parts of benzylidene-beta-aminoanthraquinone, obtained for instance by acting on betaaminoanthraquinone with benzaldehyde according to the above given recipe, are heated together with 22 parts of sulfur; the temperature is maintained at about 220230 C. until the evolution oi hydrogen sulfid ceases. The mass, after cooling, is well powdered and the excess of sulfur and some unaltered benzylidene compound eliminated from the mass by extractin it with chlorobenzene. The new dyestul remains as a yellow powder which is either very difiicultly soluble or insoluble in the usual solvents. In concentrated sulfuric acid it dissolves to a yellow solution. lVith .hydrosullite and soda-lye it produces a red vat which dyes -.cotton without a mordant red-brown tints which on ageing change to a very clear and intense yellow of very good fastness.

(2.) are parts of dibenzylidene-2J6-diaminoanthraquinone, which may be obtained by heating 2.6-diaminoanthraquinone with benzaldehyde with or without the addition of: a suitable solvent, such as naphthalene, are dissolved in about parts of naphthalene t r gether with 50 parts of sulfur; the mass is heated to 220-225 C. until the evolution of hydrogen suliid ceases. Toward the end of the reaction, even at a high temperature, the product separates partly in a crystalline form. In order to isolate the product the cooled mass is pow dered and suitably extracted, for instance by boiling it with alcohol and then with carbon bisulfid.

The new dyestuli' is thus obtained in the shape. of brilliant yellow crystals forming small leaves which melt above 300 (3.; it pulverized it forms a yellow powder which is more or less ditlicultly soluble in benzene, nitrobenzene, dichlorobenzene and glacial acetic acid to a yellow solution and which is soluble in anilin to a brown solution, whereas it dissolves in concentrated 'sulfuric acid to a yellow solution from which solution by the addition of ice are separated yellow flakes. The new dye dissolves easily in hydrosulfite and soda-lye yielding a violet-red vat from which cotton is dyed a dark violet shade which on ageing changes to an intense and clear yellow whichpossesses a very good fastnes It is obvious to those skilled in the art that our present invention is not limited to the foregoing examples or to the details given therein. Thus for instance instead of the monobenzylidene or monobenzyl derivagive the following examples, the parts be-' tive of beta ami'noanthraquinone the corresponding derivative ofv alpha-aminoanthraquinone may be employed as arentmaterial for our invention. Furt ermore, for the monobenzyl or diben'zyl or dihenzylidene derivative of 2.6- or 2.7 -diaminoanthraquinone a mixture of the respective mono or disubstituted derivatives of these two amino compounds ,may be substituted thus obtaining a mixture of several thiazole-dyes which may be directly used for dyeing purposes. Finally derivatives of alpha-aminoanthraquinone (except amino derivatives) or of beta-aminoanthraquinone may be employed in preparin the parent material, of our invention and the benzyl or benzylidene derivatives ofsuch derivatives of aminoanthraquinones may be used in carrying out the process underlying our present invention. l

Having now described our invention and the manner in which it maybe performed what we claim is, j

.1. As new articles of manufacture new vat dyes of the 'anthraquinone series possessing a so-called thiazole nucleus, the simplest member of this new class of dyes having the following formula:

which new dyes give by means of hydro- 0 sulfite and an alkali, generally speaking, a bluish red vat, from which clear and in" tense shades of a very good fastness areobtained which shades, generally speaking, vary from yellow to orange to brown, these m5 new dyes being in the pulverized shape yellow to brown powders which are diflicultly soluble in benzene, nitrobenzene, dichlorobenzene and anilin, giving a yellow to brown colored solution, and which new dyes dis- 110 solve in concentrated sulfuric acid, generally speaking, to a greenish-yellow to yellow to brown solution from which solution by the addition of ice yellow flakes are separated.

2. As a new article of manufacture the new vat dye of the anthraquinone series containing a ,so-called thiazole nucleus which new dye can beobtained by acting with sulfur in the presence 'of naphthalene 120 upon dibenzylidene 2.6 diaminoanthraquinone, this new dye being 6-benzylideneaminoanthraquinone 1.2 phenylthiazole, which new dye produces on cotton from a y clear and intense yellow 125 suitable vat a ver Shade of a verygood fastness, and this new dye being in the pulverized shape a yellow powder melting above 300 C. whiehdye is more or less diflieultly soluble in benzene, nitrobenzene, dichlorobenzene and glacial 0 acetic acid to a yellow solution and soluble set our hands in presence of two subscribing .in anilin to abrown solution, this new dye witnesses. dissolving in Concentrated sulfuric acid to WILHELM HERZBERG. a yellow solution, from which solution by WALTER BRUCK. 9 5 the addition of 'ice'yellow flakes are sepa- Witnesses: 1

rated. 9 HENRY HASPER,

In testimony whereof we-have hereunto WOLDEMAB HAm 'r. 

